highlight 12 2017

We have recently investigated a novel alkyne-allene photochemical reaction in a donor-acceptor charge-transfer dyad. Application of three broadband femtosecond techniques: transient IR (left), fluorescence upconversion (middle) and electronic transient absorption (right) gives a detailed picture of the electronic and structural rearrangements taking place upon photoexcitation of this system. The transformation of the alkyne spacer into an allene moiety is accompanied by a twist and a rehybridization resulting in a Twisted and Rehybridized Intramolecular Charge Transfer State (‘TRICT’). In this particular case, isomerization leads additionally to the formation of a charge-separated structure. These results pave a new way of generating allene-type intermediates in chemical reactions. For detailed information, please, check http://pubs.acs.org/doi/10.1021/jacs.7b09591 or watch the short video presentation at ACS ActiveSlides http://pubs.acs.org/doi/suppl/10.1021/jacs.7b09591.

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Eric Vauthey

Physical Chemistry Department - Sciences II - University of Geneva
30, Quai Ernest Ansermet - CH-1211 Geneva 4 (Switzerland)

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